Heterocyclically substituted monohalogeno-1, 3, 5-triazines



United States Patent Oifice 3,407,201 HETEROCYCLICALLY SUBSTITUTED MONO-HALOGENO-LSfi-TRIAZINES Christian Luethi, Munchenstein, Hans RudolfBiland,

Basel, Max Schellenbaum, Riehen, and Max Duennenberger, Frenkendorf,Basel-Land, Switzerland, assignors to Ciba Limited, Basel, Switzerland,2 Swiss company No Drawing. Filed Jan. 28, 1966, Ser. No. 523,552 Claimspriority, application Switzerland, Feb. 4, 1965, 1,541/ 65 12 Claims.(Cl. 260-248) I ABSTRACT OF THE DISCLOSURE New heterocyclicallysubstituted monohalogeno-1,3,5- triazines are provided which may berepresented by the formula Halogen ir-n wherein A contains at least onering nitrogen atom and represents an aromatic ring system made up of 1to 3 six-membered rings, which are fused in the case of ring systemscontaining 2 r 3 rings, and is linked through a ring carbon atom with X;X represents a divalent hetero-atom bridge member chosen from O, S-, and--NQ-, where Q stands for hydrogen or a lower alkyl group and Wrepresents a monovalent, aliphatic, heterocyclic,- aromatic oraraliphatic residue which is linked through a carbon atom with thetriazine ring and contains no more than 20 carbon atoms.

The compounds of the invention are especially useful as fungicides andbactericides.

The present invention provides new heterocyclically substitutedmonohalogeno-1,3,5-triazines having a fungicidal and at the same time abactericidal action, and includes also their use as well as processesfor their manufacture.

The compounds of this invention correspond to the general Formula 1 HalHa WC where Hal represents a halogen atom, A contains at least one ringnitrogen atom and represents an aromatic ring system made up of 1 to 36-membered rings, which are fused in the case of the Z-membered or3-membered ring systems, and is linked through a ring carbon atom withX; X represents a divalent hetero-atom bridge member chosen from -O-,S-, and NQ, where Q stands for hydrogen or a lower alkyl group(preferably hydrogen), W represents a monovalent, aliphatic,heterocyclic, aromatic or araliphatic residu which is linked through acarbon atom with the triazine ring and contains no more than 20 carbonatoms.

The residues A and W in the above formula may contain furthersubstituents. Preferred products of this in- 3,407,201 Patented Oct. 22,1968 vention within the scope of the above formula are new triazinederivatives of the general formula:

2 UC N 1A1 where X represents a divalent hetero-atom bridge memberchosen from O, S, and NH-; A con- Z %NC Q N Y N=C I ia-A:

where A contains 1 or 2 ring nitrogen atoms and represents an aromaticring system consisting of one or two fused 6-membered rings boundthrough a ring carbon atom with X X represents a divalent hetero-atombridge member chosen from --O and S, and Z and Y each represents ahydrogen atom, an alkyl or alkoxy group containing 1 to 6 carbon atoms,a halogen atom, a lower alkylated amino group, or Y or Z is a phenylgroup, or Y+Z may form together with the phenyl group, a naphthyl ring.

Compounds obtained by a preferred variant of the present invention arethose of 'the formula:

where A contains 1 or 2 ring nitrogen atoms and represents an aromaticring system consisting of two fused 6-membered rings bound through aring carbon atom with the bridge member O; Z and Y represent hydrogen,an alkyl or alkoXy group containing 1 to 6 carbon atoms, halogen, anamino group alkylated with alkyl groups containing 1 to 8 carbon atoms,or Y or Z represents a phenyl radical, or Y+Z represent, together withthe phenyl group, a naphthyl ring.

The new triazine derivatives of the general Formula 5 also deservespecial mention:

where Z and/or Y represent a hydrogen atom, an alkyl or alkoxy groupcontaining 110 6 carbon atoms, a halogen atom, an alkylated amino groupcontaining up to 6 carbon atoms or Z alone represents a phenyl group,and the residues R represent hydrogen atoms or halogen atoms or each Ralone represents an alkyl group containing 1 to 4 carbon atoms.

Of special value are those compounds corresponding to the Formula 4 inwhich Y is hydrogen and Z as Z when it stands in para-position to thebond of the phenyl radical with the triazine ring, represents a hydrogenatom, an alkyl or alkoxygroup containing 1 to 4 carbon atoms, a phenylgroup, a dialkylamino group whose alkyl residues contain 1 to 4 carbonatoms, or a chlorine or bromine atom.

The cyclic system A in the Formula 4 is preferably a quinoline ringwhich is bound in position 8 and may be further substituted, so that aSpecific valuable type of compound is represented by a formula:

where Z has the above meaning and the residues R are hydrogen or halogenatoms, or in each case one R alone may stand for an alkyl groupcontaining 1 to 4 carbon atoms, or for a nitro, nitroso or sulpho group.

As examples of compounds belonging to the individual types of compoundscorresponding to the above formulae there may be mentioned those inwhich the residue A or A respectively in the structural element of theformula,

( Hal which is essential to the present invention, belongs to one of thefollowing types of compounds:

(a) Quinolines-the isomeric hydroxyquinolines, especially themonohydroxyquinolines, also polyhydroxyquinolines, for example2,4-dihydroxyquinoline, the isomeric aminoquinolines andmercaptoquinolines, for example 2- and 8-mercaptoquinolines (b)Quinaldinesfor example 4- and 8-hydroxyquinaldine, 4- and8-aminoquinaldine (c) Isoquinolines-such as -hydroxy-isoquinoline, 4-and S-aminoisoquinoline (d) Cinnolines (e) Phthalazines (f)Quinazolines-such as 4-hydroxyquinazoline (g) Quinoxalinessuch as2,3-quinoxaline-diol or -dithiol (h) Acridinesfor examplel-hydroxyacridine or 9-aminoacridine (i) Phenazines-such asl-hydroxyphenazine or 4-aminophenazine (k) Pyridinesfor example 2-, 3-and 4-hydroxypyridine and the corresponding aminopyridines, 2- or4-mercaptopyridines or nicotinic acid (1) Pyridazinesfor example3,6-dihydroxypyridazine or amino or mercapto analogues thereof (m)Pyrimidines-for example 2- or 4-hydroxypyrimidine ordihydroxypyrimidines, Z-aminopyrimidine, 2-mercaptopyrimidine or6-methylthiouracil,

(r1) Pyrazines.

4 From among the practically specially valuable hydroxyquinolines and-quinaldines the following may be mentioned as non-limitative examples:

(a) Haogen derivatives:

a a @1 3 @yy 01 \M O H p H (II) nn (Ill (])H B r Q3 013 H a H (IV) (V)Br Cl CH3 OH $11 H (VII) (VIII) (IX) I G1 I l (b) Sulphonic acids:

sloaH 8'0 311 I N N O H O H (XII) (XIII) (c) Carboxylic acids:

('3 O 0 H (311 (|)lI C O O I! N OH N 00011 C1 N (XIV) (XV) (XVI) (d)Nitro compounds:

O N X 0 II O H xvrr xvnr) X=H, Cl, Br, I

(e) Alkoxy compounds:

HaCO- with a compound of the formula (9) H-XA where W, X and A have thesame meanings as in Formula 1 and Hal stands for a chlorine or bromineatom.

According to a particularly advantageous method the triazine derivativescorresponding to the Formulas 2, 3 or 4 may be manufactured by reactingone mol of a 2-aryl-4,6-dichloro-l,3,5-triazine with one mol of anN-heterocyclic phenol or mercaptan. This reaction may be carried out inan aqueous medium, that is to say in a medium containing apart fromwater also water-soluble organic solvents that are chemically inerttowards the reactants, such for instance as acetone or dioxan,advantageously in the presence of an acid acceptor, for example aninorganic base, such as an alkali or alkaline earth metal hydroxide oralkali metal carbonate.

According to another variant this reaction may be carried out in anorganic solvent that is chemically inert towards the reactants andpossesses an adequate solving property, for example, chlorobenzene,dichlorobenzene, nitrobenzene or the like; in these cases the reactionis advantageously performed in the presence of a Lewis acid, such asaluminum chloride, tin tetrachloride, boron trifluoride or similarsubstances having a catalytic elfect, or working up may be performedwith an acid acceptor as mentioned above.

Finally, it is also possible to react the reactants in a melt in theabsence of a solvent, if desired in the presence of a Lewis acid or ofan acid acceptor as mentioned above. The N-heterocyclic phenols to beused in the reaction may be used directly in the phenol form or in theform of their alkali metal salts. Normally, the reactants are reacted inequimolecular proportions, but this does not exclude the use of aslightly greater or smaller proportion in special cases. The reactiontemperature depends on the reactivity of the components and the reactionmedium chosen and is advantageously within the range from C. toapproximately the boiling point of the solution or reaction mixture; inthe case of melts it may be up to about 280 C., provided the reactantshave adequate thermostability. The amount of acid acceptor, if such isused, corresponds advantageously at least to the amount equivalent tothe hydrogen halide to be eliminated. Lewis acids are generally used inan amount from 0.1 to 2.5 equivalents.

According to a preferred variant, which is particularly suitable for thereaction of hydroxyor mercapto-quinolines with2-aryl-4,6-dichloro-1,3,S-triazines, for example, the reactants (a) arereacted in a solution of a chlorobenzene in the presence of 0.1 to 2.5equivalents of aluminum chloride or (b) in a chlorobenzen ormethylbenzene solution in the presence of an equivalent amount of anacid acceptor.

According to one variant of the process for the manufacture of compoundsof the Formula 1 a compound corresponding to this formula is firstsynthesized by one of the methods referred to above and then the halogenatom, which is preferably attached in position 4 on the triazine ring,is exchanged for another halogen. It is possible, for example, toprepare in this manner the valuable fluoro compounds of this type.

The compounds accessible by the afore-mentioned Wesses, especially thetriazine derivatives of the Formulae 4, 5 and 6, display a distinctantibacterial activity combined with a high antimycotic effect.

In this connection special attention is directed to the use of compoundsof the general formula (10) Hal @r ar Z: N

where Hal represents a halogen atom and Z a hydrogen atom, a halogenatom or an alkyl group containing 1 to 4 carbon atomsfor protectingorganic materials from fungi and bacteria, as well as the use ofcompounds of the general formula where Hal represents a halogen atom and2,; a hydrogen atom, a halogen atom or an alkyl or alkoxy groupcontaining 1 to 4 carbon atoms for protecting organic materials fromfungus attacks.

The broad antibacterial activity spectrum observed in this connection,which with many compounds extends to both Gram-positive andGrxammegative bacteria, is particularly unexpected. Of special advantagein the application is the absence of odours and colours in the compoundsof this invention.

Thus, the present invention includes also the use of the new compoundsin general pest control. The antibacterial compounds may be applied in avery wide sphere, especially for protecting organic substrates fromattacks by destructive and pathogenic (including phytopathogenic)micro-organisms. Accordingly, the antimicrobial substances are suitablefor use as preservatives and as disinfectants for textile materials andtechnical products of all descriptions, in plant protection, inagriculture, in veterinary medicine and in cosmetics.

From among technical products that can be preserved with the aid of thenew compounds there may be mentioned the following examples: Textileauxiliaries and improving agents, glues, binders, paints, colour andprinting pastes an dsimilar preparations based on organic or inorganicdyestulfs or pigments, including those which contain casein or otherorganic compounds. Wall and ceiling paints, for example such as containa protein paint binder, can be protected from attacks by pests byadmixture with the new compounds. The new products are also suitable foruse in timber protection.

Furthermore, the new compounds may be used for providing fibres andtextile materials with a preserving and disinfecting finish, and thesefibres may be natural or man-made fibres. 0n application to such fibresthe products of this invention act permanently against harmful(including pathogenic) organisms, for example fungi and bacteria. Theaddition of the new compounds may take place before, during or afterthese textile materials are or have been treated with other substances,for exarlrgple colour or printing pastes, dressing agents or the li e.

Textile materials treated in this maner are also protected from theappearance of perspiration odour as caused by micro-organisms.

The new compounds may also be used to preserve the products of thecellulose and paper industries, inter alia to prevent the known slimeformation due to micro-organisms in the machines used for themanufacture of paper.

Furthermore on incorporation of the compounds of this invention in washactive or surface active substances there are obtained detergents andcleansing agents having an excellent antibacterial or antimycoticeffect. The compounds of the general formulae defined above may, forexample, be incorporated in soaps or combined with soap-free,wash-active or surface-active substances, or they may be combined withmixtures of soaps and soapfree wash-active substances, without losingany of their antimicrobial activity in these combinations.

Cleansing agents containing the compounds of the above formulae may alsobe used in industryand in the household, and also in the food industry,for example in dairies, breweries and abattoirs. The new compounds mayalso form an ingredient of preparations used for cleansing and/ordisinfection in hospitals and in the surgery The action of the compoundsof this invention may also be utilized to provide plastics withpreserving and disinfecting dressings. When plasticizers are used it isof advantage to add the antimicrobial substance in the form of asolution or dispersion in the plasticizer to the plastic material, itbeing of value to ensure as uniform a distribution as possible of thesubstance in the plastic material. Plastic materials havingantimicrobial properties may be used in a variety of objects for generaluse which are desired to be resistant to pathogens of all kinds, forexample bacteria and fungi, for example in doormats, bathroom curtains,seats, treads in swimming baths, wall coverings or the like. Byincorporation with suitable wax and polishing preparations there areobtained preparations for the care of floors and furniture having adisinfectant action.

The antimicrobial ingredients may be applied to the textile materials tobe protected in a wide variety of ways, for example by impregnating orspraying them with solutions or suspensions containing theabove-mentioned compounds as active ingredient. The amount of activeingredient used may vary according to the ultimate purpose from 1 to 30g. of active substance per litre of treating liquor.

In most cases textile materials of natural or synthetic origin areadequately protected from attacks by fungi and bacteria by a content of0.1 to 3% of active substance. The active substances mentioned may beused in conjunction with other textile auxiliaries, such as dressingagents, anticrease finishes and the like.

The forms in which the compounds of this invention are applied maycorrespond to those conventionally used for pesticides; for example,preparations containing the said active substances may further containadditives such as vehicles, solvents, diluents, dispersants, wettingagents, adhesives or the like, as well as other pesticides.

Unless otherwise indicated, parts in the following examples are byweight.

Example 1 A solution of 29.0 parts of S-hydroxyquinoline in 100 parts byvolume of dioxan is stirred into a solution of 48.0 parts of2-para-tolyl-4,6-dichloro-1,3,5-triazine in 500 parts by volume ofdioxan and 30 parts of water. 110 parts of a 1.82 N-sodium hydroxidesolution are dropped in at 50 to 60 C. at a rate such that the pH valuedoes not rise above 7. The reaction mixture is then poured over 2000parts of ice water and the resulting suspension is stirred in for 1hour. The product of the formula Hacis filtered oif, rinsed with 500parts of water and dried. The yield amounts to about 66 parts. Theproduct obtained by recrystallization from methylenechloride+ methanolforms colourless crystals and melts at 193- 195 C.

C H ON Cl.-Calculated: C, 65.43; H, 3.76; 'N, 16.06%. Found: C, 65.28;H,3.88; N, 16.19%.

Example 2 13.0 parts of 2-(4'-chlorophenyl)-4,6-dichloro-1,3,5- triazineand 7.3 parts of 8-hydroxyquinoline are dissolved in 120 parts ofdichlorobenzene, and 7.4 parts of anhydrous aluminium chloride are thenstirred in at 10 C. The reaction mixture is heated for 20 hours at 40 C.and then poured over 1000 parts of ice water. The aqueous phase isseparated and the dichlorobenzene solution washed with water and thesolvent expelled with steam. The residue is filtered off and dried. Theyield amounts to about 13 parts. The product of the formula is purifiedby two recrystallizations from methylenechloride+petroleum ether andmelts at 192194 C.

C H ON Cl .Calculated: C, 58.56; H, 2.73; N, 15.18%. Found C, 58.28; H,2.80; N, 15.29%.

Example 3 is obtained in a yield of about 25 parts. For purification theproduct may be recrystallized from methylenechloride-I-methanol. Thepure compound melts at 215- C H ON C1 B1' .Calculated: C, 41.02; H,1.53; N, 10.63%. Found: C, 40.88; H, 1.39; N, 10.81%.

Examples 4 to 25 The compounds of the formula N, ealc.; N, found TABLE IAnalysis- Z1= M.I., C.

C, calc.; H, calc.: 0, found H, found Ex. Formula A2= No. No.

shown in the following Table I were prepared as described in Example 1:

(119K110 N4 C14 ONHHON 4C CmHuONACh 7 M3 mm mm m CnHmONl C14 (ll-O01CROHHONICIZ TABLE ICntinued Analysis- Ex Formula A2= Z1= M.P., C. No.No. C, ca1c.; H, cale.; N, calc.; 0, found H, found N, found (32) C1HaCO- 197-199 57.16 3.03 14.03 57. 03 3. 07 13. 87

CmHuOzNlCh N I 21 (33) I Cl HsCO- 222-224 43. 46 2. 11 10. 67 43. 36 1.94 10. 61

Cn n02N4Cl2I N I CmHuONACl o N I 23 OIH Cl 290 48. 12 2. 24 12. 47 48.05 2. 24 12. 32

C1a |u04N|SCl N l 24 (36) Cl 257-253 49. 35 1. 84 12. 79 C1 49. 11 1. 7512. 54

CmHsONACll Cl- CIQ QOaNaCh N l Examples 26 to 40 pared as described inExample 1. The symbols A, X and The examples listed in the followingTable II were pre- W have the same meanings as in Formula 1.

TABLE II Analysis Ex. N0. Formula A= X= W= M.P., C.

No. C, calc.; H, calc.; N, calm;

0, found H, found N, found C1s 1nN4S CI:

TABLE IIontinued Analysis Ex. No. Formula A= X= W= M.P., C.

No. C, cale; H, cale.; N, calm;

0, found H, found N, (ound (47) Cl -O-- (CzHmN 172-173 60.80 4. 66 15.4160.58 4.51 15. 39

CuHnONlCh l I I l HI N 36 (48) O 200-201 59.18 2. 79 17.25 58.95 2. 9317.15 0 CnHaoa scl N I 37 (49) Cl O 211-212 53. 51 2. 25 15. 53.36 2.1515. 39 0 culis sNaCla S C1oHnON4SCl N I S cuHsoNlsclz 40 (52) -O -OH170-172 65. 02 3.27 13. 98 65. 86 3. 25 13. 80

CflHUOiNlCl J Examples 41 to 48.Antibacterial action in the dilutiontest In each test 20 mg. of the active substances described in theforegoing examples were dissolved in 10 m1. of propyleneglycol ordimethylsulphoxide (=0.2% of active substance). Of these soltuions 0.25ml. each was added to 4.75 ml. of sterile glucose broth (=100 parts permillion) and the content of each test tube was immediately diluted inthe tube at the ratio of 1:10. After inoculation with Staphylococcusaurelts and, respectively, Escherichia coli, the cultures were incubatedfor 48 hours at 37 C. (test for bacteriostatic elfect). After allowingthe cultures to grow for 24 hours, the amount retained by a loop ofplatinum wire from each tube was smeared over a glucose a-gar plate andlikewise incubated for 24 hours at 37 C. (test for bactericidal effect).

After the times mentioned the minimum inhibitory concentration values(parts per million) shown in the following Table III were recorded.

Fungicidal effect in the dilution test.Solutions of the activesubstances described in the foregoing examples in propyleneglycol ordimethylsulphoxide in concentrations descending from 500 to 1 part permillion were introduced in tubes containing sterile beer wort solutionof 10% strength. After inoculation with Aspergillus niger, and,respectively, Rhizopus nigricans, the cultures were incubated for 72hours at 25 C. (test for fungistatic effect). The minimum inhibitoryconcentration values (parts per million) are listed in Table III.

.21 Examples 49 to 65.-Effect against bacteria and fungi, measured asthe minimal inhibitory concentration in the dilution test 22 strength ofthe active substances in dimethylsulphoxide, dilution series, in whicheach member was a tenth of the preceding member were prepared. Bycombining the two series the following continuous dilution series wasobtained. 1000, 300, 100, 30, 10, 3 p.p.m. and so forth.

After inoculation and incubation as described in columns 17, 18 theminimal inhibitory concentrations for the bacteriostatiic and thefungistatic effort each were determined.

TABLE IV Minimum inhibitory concentration (p.p.m.) Example FormulaBaeterlostatic effect Fungistatlc etiect Number Staph. aureusEscherichia Aapcrqfll. Rhizopul colt maer niaricam 49 &0 so 10 10 51 magso so sa 10o so TABLE IV-Confinued Minimum inhibitory concentration(p.p.m.)

Bacteriostatic efiect Funglstatic eflect Formula Example NumberStuph.aureua Escherichia Asperaill. Rhizopus ooh Myer niaricam TABLEIV'Continued Minimum inhibitory concentration (p p.m.)

Example Formula Bacteriostatic efieet Funglstatic effect Number Staph.aureus ESChCfZChIG Asperazll. Rhtzopus colt m'yer nigricam C -0 s u N /N\(IZ; N

- 01 l I N\ What is claimed is: an alkoxy group each containing 1 to 6carbon atoms, 1. The triazine compound of the formula halogen, a lower:alkylated ammo group, and Y together with Z fonming together with thephenyl group, a naphthyl 01 ring 4. The triazine compound of the formulaU-C N 01 N=? Z1 /N-- where X represents a divalent hetero-atom bridgemem- Y, =o ber selected from the group consisting of -O--, S-, and-NH--, A contains 1 to 2 cyclic nitrogen atoms and represents anaromatic ring system which consists of one N to two six-membered ringsand is bound through a ring carbon atom with X and U represents a memberselected R1 from the group consisting of phenyl, phenyl substituted by amember selected from the group consisting of alkyl containing 1 to 6carbon atoms, alkoxy containing 1 to 6 carbon atoms, halogen, lowerlalkylated amino and phenyl, naphthyl, fury] and thienyl.

2. The triazine compound of the formula here A contains 1 to 2 ringnitrogen atoms and reresents an aromatic ring system consisting of oneto two fused G-membered rings bound through a ring carbon atom with X Xrepresents a divalent hetero-atom bridge member selected from the groupconsisting of -O and -S, and Y is :a phenyl group, Z and Y eachrepresent a member selected from the group consisting of hydrogen, analkyl group, an alkoxy group each containing 1 to 6 carbon atoms, ahalogen atom, a lower alkylated amino group, and Y together with Zforming together with the phenyl group, a naphthyl ring.

3. The triazine compound of the formula where A;, contains 1 to 2 ringnitrogen atoms and represents an aromatic ring system which consists oftwo fused o-membered rings and is bound through a ring carbon atom withthe bridge member O-, Y represents a phenyl group, Z and Y eachrepresent a member selected from the group consisting of hydrogen, analkyl group,

where Z and Y each represent a member selected from the group consistingof a hydrogen atom, an alkyl group and an alkoxy group each containing 1to 6 carbon atoms, a halogen atom, an alkylated amino group containingup to 6 carbon atoms and Z alone represents a phenyl group, and theradicals R each represent a member selected from the group consisting ofa hydrogen atom and a halogen atom, each R alone represents an alkylgroup containing 1 to 4 carbon atoms.

5. The triazine compound according to claim 3, where Y representshydrogen and Z, as Z in para-position to the bond of the phenyl radicalwith the triazine ring, represents a member selected from the groupconsisting of a hydrogen atom, an alkyl group and an alkoxy group eachcontaining 1 to 4 carbon atoms, a phenyl group, a dialkylamino gnoupwhose alkyl groups contain 1 to 4 carbon atoms, a chlorine and aibromine atom.

6. The triazine compound of the formula where Z represents a memberselected from the group consisting of a hydrogen, an alkyl group and analkoxy group each containing 1 to 4 carbon atoms, a phenyl group, adialkylamino group whose alkyl radicals contain 1 to 4 carbon atoms, achlorine and a bromine atom, and the radicals R each represent a memberselected from the group consisting of hydrogen and halogen each R alonerepresenting a member selected from the group consisting of an alkylgroup containing 1 to 4 carbon atoms, a nitro, a nitroso and a sulphogroup.

27 28 7. The compound of the formula 10. The compound of the formula ClBr Br 01 N N l O? r 5 1 t- N\ /N N\ /N o N c N 51 51 8. The compound ofthe formula 10 11. The compound of the formula N N "f W if l l 2 l \C Nc N J11 V ('11 9. The compound of the formula 12. The compound of theformula 20 I- 01 C1 c1 01 I F W a 9- l 51 K I 2 K K) c N o N $1 51References Cited UNITED STATES PATENTS 3,293,249 12/1966 Biland et al.260248 HENRY R. JILES, Primary Examiner.

I. M. FORD, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,407,201 October 22, 1968 Christian Luethi et al.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 25, lines 63 to 69, the right-hand portion of the formula shouldappear as shown below:

Column 26, lines 57 to 65, the lower right-hand portion of the formulashould appear as shown below:

Signed and sealed this 17th day of March 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR.

WILLIAM E. SCHUYLER, JR.

